Deoxybuzonamine Isomers from the Millipede <i>Brachycybe lecontii</i> (Platydesmida: Andrognathidae)

Jones, Tappey H.; Harrison, Daniel P.; Menegatti, Carla; Mevers, Emily; Knott, Kenneth; Marek, Paul E.; Hennen, Derek A.; Kasson, Matt T.; Macias, Angie M.; Lovett, Brian; Saporito, Ralph A.

doi:10.1021/acs.jnatprod.2c00077

Cited by 8 publications

(6 citation statements)

References 37 publications

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“…The sole alkaloid peak in the B. rosea extracts matched both the retention time (17.7 min) and fragmentation of one of the previously identified deoxybuzonamine isomers (1) originally isolated from B. lecontii (Fig. S4) (Jones et al 2022). The major components in the B. petasata and B. lecontii extracts were separated by 14 Da [B. petasata -M + 205 (3) and 219 (5); B. producta -M + 207 (4) and 221 (6)] and the difference between the major components of the distinct millipede species differed by 2 Da.…”

Section: Resultssupporting

confidence: 68%

“…(1), polyzonimines (2), and gosodesmine (3)] (Smolanoff et al 1975;Shear 2015;Hassler et al 2020;Jones et al 2022).…”

Section: Introductionmentioning

confidence: 99%

“…Members of the millipede order Platydesmida have intriguing qualities such as egg brooding, and other quasisocial traits, and are almost exclusively associated with various fungal taxa, which some consume in unusual circular social aggregations called pinwheels (Macias et al 2019;Wong et al 2020). All of the species of the Platydesmida with characterized chemical secretions, and its evolutionary sister Polyzoniida (Rodriguez et al 2018), have disparate heterocyclic terpenoid alkaloids, including Brachycybe lecontii from the eastern U.S. that produces 1 and Gosodesmus claremontus from California and Oregon that produces 3 (Hassler et al 2020;Jones et al 2022) (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

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The Chemistry of the Defensive Secretions of three species of millipedes in the genus Brachycybe

Banks,

Funkhouser,

Macias

et al. 2024

Preprint

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Millipedes have long been known to produce a diverse array of chemical defense agents that deter predation. These compounds, or their precursors, are stored in high concentration within glands (ozadenes) and are released upon disturbance. The subterclass Colobognatha contains four orders of millipedes, all of which are known to produce terpenoid alkaloids—spare the Siphonophorida that produce terpenes. Although these compounds represent some of the most structurally-intriguing millipede-derived natural products, they are the least studied class of millipede defensive secretions. Here, we describe the chemistry of millipede defensive secretions from three species of Brachycybe: Brachycybe producta, Brachycybe petasata, and Brachycybe rosea. Chemical investigations using mass spectrometry-based metabolomics, chemical synthesis, and 2D NMR led to the identification of five alkaloids, three of which are new to the literature. All identified compounds are monoterpene alkaloids with the new compounds representing indolizidine (i.e. hydrogosodesmine) and quinolizidine alkaloids (i.e. homogosodesmine and homo-hydrogosodesmine). The chemical diversity of these compounds tracks the known species phylogeny of this genus, rather than the species geographical proximity. The indolizidines and quinolizidines are produced by non-sympatric sister species, B. producta and B. petasata, while deoxybuzonamine is produced by another set of non-sympatric sister species B. rosea and Brachycybe lecontii. The fidelity between the chemical diversity and phylogeny strongly suggests that millipedes generate these complex defensive agents de novo and begins to provide insights into the evolution of their biochemical pathways.

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Section: Resultssupporting

confidence: 68%

“…(1), polyzonimines (2), and gosodesmine (3)] (Smolanoff et al 1975;Shear 2015;Hassler et al 2020;Jones et al 2022).…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Chemistry of the Defensive Secretions of three species of millipedes in the genus Brachycybe

Banks,

Funkhouser,

Macias

et al. 2024

Preprint

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“…Unfortunately, no significant correlations at C-8 and C-14 of 3 were found in the NOESY spectrum, which did not reveal relative configurations of 3 . The DP4+ probability method was used to determine the relative configurations, which are based on the predicting chemical shifts of 13 C/ 1 H nuclei from DFT GIAO calculations and have been particularly popular in recent years. , Next, the statistical procedure was undertaken to define the suitable candidate of 3 . Therefore, calculated 1 H and 13 C NMR data of (8 R *,14 R *)- 3a were seen for better agreement with their experimental counterparts, indicated by parameters R 2 (99.82 and 99.71%) supported by DP4+ probability analysis (Table S3a,b and Figure S11a).…”

Section: Resultsmentioning

confidence: 99%

Discovery of Cadinane-Type Sesquiterpenoids from the Infected Stems of Hibiscus tiliaceus as Potential Agrochemical Fungicides

Chen,

Xu,

Yang

et al. 2024

J. Agric. Food Chem.

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Ten new cadinane-type sesquiterpenoids, named hibisceusins I−R (1−10), along with 14 known sesquiterpenoids (11−24), were acquired from the tainted stems of Hibiscus tiliaceus. Their structures were identified via spectroscopic analysis, onedimensional (1D) and two-dimensional (2D) NMR, and computer-assisted structure elucidation techniques, including infrared (IR) and mass spectrometry (MS) data. Additionally, subsequent DP4/DP4+ probability methods were used to resolve 3′s relative configurations by comparing their experimental values to the predicted NMR data. The absolute configurations of compounds 1−4 were measured through electronic circular dichroism (ECD) spectra. The ability of all isolates to inhibit the growth of five phytopathogenic fungi (Rhizopus stolonifer, Verticillium dahliae Kleb., Thanatephorus cucumeris, Fusarium oxysporum Schltdl., and F. oxysporum HK-27) was evaluated. Aldehydated sesquiterpenoids (1, 6−9, 11, 12, and 22) and a known sesquiterpenoid quinine (18) exhibited significant inhibitory activities against V. dahliae, T. cucumeris, F. oxysporum, and F. oxysporum HK-27 with minimum inhibitory concentration (MIC) values of 2.5−50 μg/mL, but all isolates remained inactive against R. stolonifer. Moreover, the effects of the isolates on the mycelial morphology were watched through scanning electron microscopy. This study revealed that aldehydated cadinane-type sesquiterpenoids could be used as novel antifungal molecules to develop agrochemical fungicides in plant protection.

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“…Compounds such as polyzonimine (1), nitropolyzonamine (2), buzonamine and various spiropyrrolizidine oximes have been reported (Meinwald et al, 1975;Röper, 1978;Wood et al, 2000;Saporito et al, 2003;Kuwahara et al, 2007). Recently, unique hydroindolizidine alkaloids and deoxybuzonamine isomers were described from the platydesmid colobognathans, Gosodesmus claremontus and Brachycybe lectonii (Hassler et al, 2020;Jones et al, 2022).…”

Section: Introductionmentioning

confidence: 99%

Alkaloids from millipedes: a re-evaluation of defensive exudates from Polyzonium germanicum

Kunert,

Pferschy-Wenzig,

Orthaber

et al. 2023

Front. Ecol. Evol.

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Millipedes are known to produce various sets of chemical compounds in exocrine defensive glands to protect themselves against predators and microorganisms. Here, we reanalyzed the gland secretion of Polyzonium germanicum, a millipede of the order Polyzoniida, by using a combination of analytical techniques such as GC-MS, LC-HRMS and high field 1D and 2D NMR spectroscopy. Previously only one compound (polyzonimine, 1) had been described, but our approach allowed us to add six compounds to the defensive chemistry of this species. Besides polyzonimine (1), we found nitropolyzonamine (2) and five new compounds: 3 (2,3-dimethyl-7’-nitro-2’,3’,5’,6’,7’,7a’-hexahydrospiro[cyclopent-2-ene-1,1’-pyrrolizine]), 4 (2,3-dimethyl-7’-nitro-2’,3’,5’,6’,7’,7a’-hexahydrospiro[cyclopentane-1,1’-pyrrolizin]-2-ene), 5 ((1Z)-8,9-dimethyl-1-(nitromethylidene)-2-azaspiro[4.4]non-8-en-7-one), and not fully identified compounds A, B. For compounds 3–5 we were able to determine the molecular constitution, for two of them (4, 5) we were able to give relative configurations. Overall, the combination of advanced analytical techniques applied herein allowed detailed insights into the defensive chemistry of P. germanicum with a low number of individuals needed for analysis and without prior compound isolation.

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Deoxybuzonamine Isomers from the Millipede Brachycybe lecontii (Platydesmida: Andrognathidae)

Cited by 8 publications

References 37 publications

The Chemistry of the Defensive Secretions of three species of millipedes in the genus Brachycybe

The Chemistry of the Defensive Secretions of three species of millipedes in the genus Brachycybe

Discovery of Cadinane-Type Sesquiterpenoids from the Infected Stems of Hibiscus tiliaceus as Potential Agrochemical Fungicides

Alkaloids from millipedes: a re-evaluation of defensive exudates from Polyzonium germanicum

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